The present invention pertains to novel methods and compositions for inhibiting polymerization in industrial plant streams which contain reactive light olefins, thereby preventing fouling of processing equipment and of product in storage tanks. Particularly, the invention pertains to the use of a combination of phenylenediamines and nitroxides to prevent undesired polymerization in reactive light olefins.
Industrial plant streams and processes which contain reactive light olefins are plagued with fouling problems due to unwanted polymerization. Examples of such plant streams and processes are hydrocarbon cracking processes in which light olefins are generated, industrial distillation processes of light olefin monomers, hydrogenation of light olefins and acetylenic compounds, and the like. Particular examples of such plant streams are depropanizer and debutanizer bottoms, light olefins typically generated in ethylene crackers. Such processes employ elevated temperatures which results in unwanted polymerization of the light olefin monomers. This unwanted polymerization results in the formation of deposits, or fouling, in distillation columns and other equipment such as heat transfer surfaces, reactor beds, reboilers, process lines, compressors, etc.
Fouling of the equipment or product during the stages of handling, processing, purification, and storage results in significant economic loss. Formation of deposits on heat transfer surfaces reduces process efficiency, and the unwanted polymerization also results in a loss of the desired product. Eventually the process must be stopped to clean the affected equipment.
To minimize fouling, commercial antifoulants are often added at 1-100 ppm levels at some point in the industrial process. Many classes of antifoulants are known, including phenylenediamines, hydroxylamines, nitroxides, and hindered phenols. However, fouling problems in reactive light olefin plant streams are not completely solved and industry continues to search for better solutions as well as for more cost effective ways to attack this problem.
Unexpectedly, the combination of phenylenediamines with nitroxides is found to be synergistic in its ability to prevent fouling in reactive light olefin streams. The activity of this combination exceeds that of state-of-the-art antifoulants. The state-of-the-art is described in the patents below, the relevant parts of which are incorporated herein by reference.
U.S. Pat. No. 4,670,131 discusses the use of any stable free radical to prevent polymerization in unsaturated organic feed streams. Specifically claimed is the prevention of fouling in olefinic feed streams by incorporation of a nitroxide at less than 700 ppb.
U.S. Pat. No. 5,282,957 discloses the use of hydroxyalkylhydroxylamine compounds to inhibit polymerization of hydrocarbon fluids containing dissolved oxygen.
U.S. Pat. No. 5,396,005 discloses the combination of a methoxyphenol, either eugenol or 2-t-butytl-4-hydroxyanisole, with a phenylenediamine to prevent polymerization of ethylenically unsaturated monomers.
U.S. Pat. No. 5,416,258 discusses the method of inhibiting polymerization of a butadiene-containing stream by the addition of a combination of a phenylenediamine and a hydroxytoluene compound.
The following patents teach the use of nitroxides as inhibitors in combination with coadditives to prevent polymerization in various systems. The coadditives include phenylenediamines.
JP 93/320217 discloses the use of nitroxides with coadditives in methacrylic acid. The coadditives are phenothiazines, aromatic amines, and phenols.
DE 19609312 A1 and related WO 97/32833 disclose the use of nitroxides as inhibitors for monomers in which the vinyl group is attached to a heteroatom. The compositions may additionally contain one or more costabilizers of the group of phenothiazines, quinones, hydroquinones and their ethers, hydroxylamines or phenylenediamines.
U.S. Pat. No. 5,711,767 discloses the use of nitroxides to prevent oxidative degradation and gum or deposit formation in gasoline. A costabilizer may also be employed which is selected from the group consisting of an aromatic amine, a phenolic antioxidant or a mixture of an aromatic amine and a phenolic antioxidant.
The synergistic activity of the combination of phenylenediamines with nitroxides towards preventing fouling in reactive light olefins is unknown. The superior performance of this particular combination to prevent premature polymerization in light olefins is not disclosed or suggested in the prior art.
The present invention pertains to novel methods and compositions for preventing premature polymerization in industrial plant streams and processes containing reactive light olefins. The use of these novel methods and compositions prevents fouling of equipment and product during handling, processing, purification, and storage.
The novel compositions of this invention, stabilized against premature polymerization, comprise
a) a light olefin monomer, and
an effective polymerization inhibiting amount of
b) at least one phenylenediarnine of the formula I 
wherein R1, R2, and R3 are the same or different and are hydrogen, straight or branched chain alkyl of 1 to 20 carbon atoms, straight or branched chain alkyl of 1 to 20 carbon atoms which is substituted by one to three aryl groups, aryl of 6 to 12 carbon atoms, or aryl of 6 to 12 carbon atoms which is substituted by one to three alkyl groups of 1 to 6 carbon atoms; and
c) at least one nitroxide of the formula II 
wherein R4 and R5 are independently alkyl of 1 to 4 carbon atoms or are together pentamethylene; and Z1 and Z2 are each methyl or Z1 and Z2 together form a linking moiety which may or may not contain heteroatoms or carbonyl groups and which additionally may be substituted by hydroxy, cyanohydrin, amino, alkoxy, amido, ketal, carboxy, hydantoin, carbamate, or a urethane group.
The novel method of this invention comprises
adding to a reactive light olefin an effective polymerization inhibiting amount of
b) at least one phenylenediamine of the formula I 
wherein R1, R2, and R3 are as defined previously; and
c) at least one nitroxide of the formula II 
wherein R4, R5, Z1, and Z2 are as defined previously.
The phenylenediamines of this invention have at least one Nxe2x80x94H group. Preferred examples of phenylenediamines of this invention include N-phenyl-Nxe2x80x2-methyl-1,4-phenylediamine, N-phenyl-Nxe2x80x2-ethyl-1,4-phenylediamine, N-phenyl-Nxe2x80x2-n-propyl-1,4-phenylediamine, N-phenyl-Nxe2x80x2-isopropyl-1,4-phenylediamine, N-phenyl-Nxe2x80x2-n-butyl-1,4-phenylediamine, N-phenyl-Nxe2x80x2-iso-butyl-1,4-phenylediamine, N-phenyl-Nxe2x80x2-sec-butyl-1,4-phenylediamine, N-phenyl-Nxe2x80x2-t-butyl-1,4-phenylediamine, N-phenyl-Nxe2x80x2-n-pentyl-1,4-phenylediamine, N-phenyl-Nxe2x80x2-n-hexyl-1,4-phenylediamine, N-phenyl-Nxe2x80x2-(1-methylhexyl)-1,4-phenylediamine, N-phenyl-Nxe2x80x2-(1,3-dimethylbutyl)-1,4-phenylediamine, N-phenyl-Nxe2x80x2-(1,4-dimethylpentyl)-1,4-phenylediamine, N-phenyl-Nxe2x80x2,Nxe2x80x2-dimethyl-1,4-phenylenediamine, N-phenyl-Nxe2x80x2,Nxe2x80x2-diethyl-1,4-phenylenediamine, N-phenyl-Nxe2x80x2,Nxe2x80x2-di-n-butyl-1,4-phenylenediamine, N-phenyl-Nxe2x80x2,Nxe2x80x2-di-sec-butyl-1,4-phenylenediamine, N-phenyl-Nxe2x80x2-methyl-Nxe2x80x2-ethyl-1,4-phenylenediamine, N,Nxe2x80x2-dimethyl-1,4-phenylenediamine, N,Nxe2x80x2-diethyl-1,4-phenylenediamine, N,Nxe2x80x2-di-isopropyl-1,4-phenylenediamine, N,Nxe2x80x2-di-iso-butyl-1,4-phenylenediamine, N,Nxe2x80x2-di-sec-butyl-1,4-phenylenediamine, N,Nxe2x80x2-bis(1,4-dimethylpentyl)-1,4-phenylenediamine, N,Nxe2x80x2-bis(1,3-dimethylbutyl)-1,4-phenylenediamine, N,Nxe2x80x2-diphenyl-1,4-phenylenediamine, N,N,Nxe2x80x2-trimethyl-1,4-phenylenediamine, and N,N,Nxe2x80x2-triethyl-1,4-phenylenediamine.
Particularly preferred examples of phenylenediamines of this invention include N,Nxe2x80x2-di-sec-butyl-1,4-phenylenediamine, N,Nxe2x80x2-bis(1,4-dimethylpentyl)-1,4-phenylenediamine, N,Nxe2x80x2-di-iso-butyl-1,4-phenylenediamine, N,Nxe2x80x2-bis(1,3-dimethylbutyl)-1,4-phenylenediamine, N-phenyl-Nxe2x80x2-(1,4-dimethylpentyl)-1,4-phenylenediaamine, N-phenyl-Nxe2x80x2-(1,3-dimethylbutyl)-1,4-phenylenediamine, N-phenyl-Nxe2x80x2-iso-butyl-1,4-phenylenediamine, and N-phenyl-Nxe2x80x2-sec-butyl-1,4-phenylenediamine.
Nitroxides of this invention have the general formula 
wherein R4, R5, Z1, and Z2 are as defined previously.
Preferably, the nitroxides of this invention have the formulae III, IV, V, VI, VII, VIII, and/or IX. 
wherein
R is hydrogen or methyl,
n is 1 or 2 in compounds of formula III, VI, and VII,
when n is 1 in compounds of formulae III and VII,
X is hydrogen; alkyl of 1 to 18 carbon atoms; alkanoyl of 2 to 18 carbon atoms; propargyl; glycidyl; benzoyl; phenyl; alkyl or alkanoyl of 2 to 50 carbon atoms interrupted by one to twenty xe2x80x94Cxe2x95x90Cxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94 and/or xe2x80x94COOxe2x80x94 groups; alkyl of 1 to 50 carbon atoms or alkanoyl of 2 to 50 carbon atoms substituted by one to ten xe2x80x94OH and/or xe2x80x94COOY groups; alkyl or alkanoyl of 2 to 50 carbon atoms both interrupted by said xe2x80x94Cxe2x95x90Cxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94 and/or xe2x80x94COOxe2x80x94 groups and substituted by said xe2x80x94OH and/or xe2x80x94COOY groups; cycloalkyl of 5 to 12 carbon atoms; cycloalkanoyl of 6 to 13 carbon atoms; or said cycloalkyl or cycloalkanoyl interrupted by one to six xe2x80x94Cxe2x95x90Cxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94 and/or xe2x80x94COOxe2x80x94 groups; or said cycloalkyl or cycloalkanoyl substituted by one to six xe2x80x94OH and/or xe2x80x94COOY groups; or said cycloalkyl or cycloalkanoyl both interrupted by said xe2x80x94Cxe2x95x90Cxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94 and/or xe2x80x94COOxe2x80x94 groups and substituted by said xe2x80x94OH and/or xe2x80x94COOY groups,
Y is hydrogen, alkyl of 1 to 4 carbon atoms, or phenyl,
when n is 2 in compounds of formulae III and VII,
X is alkylene of 1 to 12 carbon atoms; alkylenoyl of 2 to 12 carbon atoms; alkylen-di-oyl of 2 to 12 carbon atoms; phenylene; phthaloyl; isophthaloyl; terephthaloyl; alkylene, alkylenoyl or alkylen-di-oyl of 2 to 50 carbon atoms interrupted by one to twenty xe2x80x94Cxe2x95x90Cxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94 and/or xe2x80x94COOxe2x80x94 groups; alkylene of 1 to 50 carbon atoms, alkylenoyl of 2 to 50 carbon atoms or alkylen-di-oyl of 3 to 50 carbon atoms substituted by one to ten xe2x80x94OH and/or xe2x80x94COOY groups; alkylene or alkylenoyl of 2 to 50 carbon atoms, or alkylen-di-oyl of 3 to 50 carbon atoms both interrupted by said xe2x80x94Cxe2x95x90Cxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94 and/or xe2x80x94COOxe2x80x94 groups and substituted by said xe2x80x94OH and/or xe2x80x94COOY groups; cycloalkylene of 5 to 12 carbon atoms; cycloalkylenoyl of 6 to 13 carbon atoms; cycloalkylen-di-oyl of 7 to 14 carbon atoms; or said cycloalkylene, cycloalkylenoyl or cycloalkylen-di-oyl interrupted by one to six xe2x80x94Cxe2x95x90Cxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94 and/or xe2x80x94COOxe2x80x94 groups; or said cycloalkylene, cycloalkylenoyl or cycloalkylen-di-oyl substituted by one to six xe2x80x94OH and/or xe2x80x94COOY groups; or said cycloalkylene, cycloalkylenoyl or cycloalkylen-di-oyl both interrupted by said xe2x80x94Cxe2x95x90Cxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94 and/or xe2x80x94COOxe2x80x94 groups and substituted by said xe2x80x94OH and/or xe2x80x94COOY groups,
wherein Y has the same definition as above,
in compounds of formula VI, R6 is hydrogen, straight or branched chain alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 15 carbon atoms, alkanoyl of 2 to 18 carbon atoms, alkenoyl of 3 to 18 carbon atoms or benzoyl,
Z has the same meaning as for X above for when n is 1 or 2, or Z and R6 together may form a cycloalkyl of 5 to 12 carbon atoms; cycloalkyl of 5 to 12 carbon atoms interrupted by one to six xe2x80x94Cxe2x95x90Cxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94 and/or xe2x80x94COOxe2x80x94 groups; cycloalkyl of 5 to 12 carbon atoms substituted by one to six alkyl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, xe2x80x94OH, and/or xe2x80x94COOY groups; or cycloalkyl of 5 to 12 carbon atoms both interrupted by said xe2x80x94Cxe2x95x90Cxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94 and/or xe2x80x94COOxe2x80x94 groups and substituted by said alkyl, alkenyl, xe2x80x94OH, and/or xe2x80x94COOY groups,
Y has the same meaning as above,
in compounds of formula IX, each R7 is independently hydrogen, straight or branched chain alkyl of 1 to 20 carbon atoms, or cycloalkyl of 5 to 12 carbon atoms,
each R8 is independently hydrogen, straight or branched chain alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, or a radical of the formula XI, 
where R is as defined previously and with the proviso that at least one of the R groups is of formula XI.
Particularly preferred examples of nitroxides of this invention include bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 2-ethylhexanoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl benzoate, 1-oxyl-2,2,6,6-tetrametbylpiperidin-4-yl 4-t-butyl-benzoate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)n-butylmalonate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)phthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N,Nxe2x80x2-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipamide, N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) caprolactam, N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) dodecylsuccinimide, 2,4,6-tris-[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)]-s-triazine, and 4,4xe2x80x2-ethylenebis(1-oxyl-2,2,6,6-tetramethylpiperidin-3-one).
The light olefins of this invention include hydrocarbon monomers generally having 2-6 carbon atoms. Examples are ethylene, propylene, butadiene, and isoprene.
The industrial plant streams are essentially the light olefins of this invention or they may additionally contain acetylenic compounds and/or saturated hydrocarbons. Examples of such streams are depropanizer and debutanizer bottoms which are generated in ethylene cracking processes.
The compositions of this invention are comprised of b) at least one phenylenediamine and c) at least one nitroxide, each as described supra. The inhibitor mixture may be added neat or it may be added as a solution in an appropriate hydrocarbon solvent. The components may be added separately or together as a mixture. The ratio of b) to c) employed is in the range of 1:10 to 10:1. The amount of components b) and c) necessary to prevent unwanted polymerization will depend on the temperature and duration of the particular process and may each be between 0.1 and 10,000 parts per million (ppm) based on the olefin. Preferably the amount used is between 0.1 and 100 ppm each on the olefin.
The industrial processes of this invention include any process in which a light olefin is handled or manipulated other than the intentional polymerization of the olefin. Such processes include but are not limited to hydrocarbon cracking processes, preheating, distillation, hydrogenation, extraction, etc.
The compositions and methods of this invention may also be used with other additives known to prevent fouling such as antioxidants, metal deactivators, corrosion inhibitors and the like. The stabilizer combination of this invention may be applied at any point in an industrial plant stream or process where it is effective.
Although specific embodiments of the present invention have been described in the detailed description above, the description is not intended to limit the invention to the particular forms or embodiments disclosed therein since they are to be recognized as illustrative rather than restrictive and it will be obvious to those skilled in the art that the invention is not so limited. Thus, the invention is declared to cover all changes and modifications of the specific examples of the invention herein disclosed for purposes of illustration which do not constitute departure from the spirit and scope of the invention. The embodiments of the invention in which a specific property or privilege is claimed are defined as follows.